Process for improving color developability of reversal photograph films



United States. Patent PROCESS F015 IMPROVING COLOR DEVELGP- ABILITY OF REVERSAL PHOTOGRAPH FILMS Catherine S. McCarthy, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed June 8, 1962, Ser. No. 200,910

14 Claims. (CI. 96-22) I The present invention concerns a photographic process for developing color films, and more particularly, a reversal color process for increasing the amount of dye produced in the reversal image.

It is desirable in reversal color processes to have a method for increasing the amount of dye produced in the reversal image. Such an increased dye density makes a more eflicient color reproduction system, a more accurate representation of the original scene or allows the use of thinner emulsion layers 'or less silver halide in the emulson.

It is an object of this invention to provide a new photographic reversal color process for increasing the amount of dye produced.

It is another object of this invention to provide a novel photographic process for improving the dye density in reversal images that were color-developed with developers containing color-forming materials or color couplers.

It is likewise an object of this invention to provide a novel reversal color process particularly adapted for producing magenta dye images of improved density.

These and other objects of the invention are accomplished by color-developing photographic silver halide emulsions having a vehicle of gelatin and lower alkyl acrylate-acrylic acid copolymer, the color-forming material or color coupler being in the color developer as distinguished from being in the silver halide emulsion.

The lower alkyl acrylate-acrylic acid copolymer utilized in the photographic gelatino-silver halide emulsions processed in accordance with the invention'are described in copending Houck et al. applications, U.S. Serial No. 786,- 227, filed January '12, 1959, now US. Patent 3,062,674, and US. Serial No. 139,313, filed September 19, 1961.

The subject copolymers are water soluble compositions prepared by copolymerizing a mixture of a lower alkyl acrylate and acrylic acid. The alkyl acrylates of particular interest are those-having alkyl radicals with l to 4 carbon atoms. A particularly useful alkyl acrylate is ethyl acrylate. The copolymers are suitably composed of l050 mol percent of the acrylic acid moiety. The co polymers can be utilized as such (i.e. terminating acid groups) or as Water soluble salts such as ammonium salts and alkali metal salts.

The copolymer of an alkyl acrylate and acrylic acid "ice veloping agents that can be employed in the process of the invention are the sulfonamide-substituted p-phenylenediamine disclosed by Weissberger in US. Patent No. 2,548,574, issued April 10, 1951, and the unsubstituted V p-phenylenediamines disclosed by Weissberger et al. in

US. Patent No. 2,566,271, issued August 28, 1951.

i The color developers utilized in the process of the invention are aqueous alkaline compositions that contain, in addition to a color developing agent, a color coupler. Color couplers generally belong to one of three widely known types, namely, pyrazolone couplers, phenolic couplers and open-chain ketomethylene couplers which com bine with oxidation products of color developing agents such as p-phenylenediamines to. form magenta, cyan and yellow dyes respectively. Color-forming compounds or couplers that are soluble in aqueous alkaline developing compositions are well-knownto those skilled in the present art. Typical couplers that can be suitably utilized in the color developers in the present process are listed below.

CYAN COUPLERS l S-benzenesulfoamino-l-naphthol (2) 2,4-dichloro-S-benzenesuliamino-1-naphthol (3 2,4-dichloro-- (p-toluenesulfamino -l-naphthol (4) 5-( 1,2,3 ,4-tetrahydronaphthalene-6-sulfoamino) -1- naphthol (5 2,4-dichloro-5-(4'-bromodiphenyl-4-sulfoamino) -1- naphthol (6) o- B-Naphthalenesulfonamino) -pheno1 (7) 5-(m-nitrobenzenesulfonamino)-1-naphthol (8) 5-quinoline-5-sulfonamino -1-naphthol (9 2-acety1amino-5-methylpheno1 10) 2-benzoylamino-3 ,5 dimethylphenol (l l 2-06- (p-tert. amylphenoxy) -n-butyrylamino-5- methylphenol 12) 2-ocp-tert. amylphenoxy) -n-butyrylamino-4- chlo'ro-S-methylphenol 13 2- (p-tert. amylphenoxy-p-benzoyl) amino-4-chloro- S-methylphenol (14) 2- (4"-tert. amyl-3 -phenoxybenzoylamino) -3 ,5 -dimethyl-1 -phenol l5 2-phenylacetylamino-4-chloro-5-methylphenol 16) 2-benzoylamino-4-chloro-5-methylphenol l7) 2-anilinoacetylamino-4-chloro-5 -methy1phenol l 8) 2-{4- [oc- (4--tert. amylphenoxy -n-butyrylamino] V benzoylamino}-4-chloro-5-methy1phenol 19) 2-{4'- [3 (4"-tert. amylphenoxy) -benzoylamino] benzoylamino}-4-chloro-5-methylphenol (20) 2-p-nitr0benzoylamino-4-chloro-5-methylphenol photographic silver halide developing-out emulsions composed of such silver halides as silver chloride, silver iodide,

silver bromide, silver chlorobromide, silver chloroiodide,

silver bromoiodide and silver chlorobromoiodide.

Color developers that can be utilized in the present process have previously been described in the art. Color developing agents thathave been found especially useful in our process comprise aromatic primary amines containing an amino (substituted or unsubstituted) or bydroxyl radicals. Excellent results are obtained with pphenylenediamines and including substituted derivatives containing a primary amino radical. Typical color de-' (21) 2-m-aminobenzoyl-4-chloro-5-methylphenol (22) 2-acetamino-4-chloro-S-methylphenol (23 2- (4'-sec. amylbenzamino -4-chloro-5-methylpheno1 (24) 2-(4'-n-arnyloxybenzamino)-4-chloro-5-methylphenol t MAGENTA COUPLERS (35 1-phenyl-3 -palmitylamino-5-pyrazolone amylb enzenesulfonylamino) -5- (36) -1-phenyl-3-(p-sec.

pyra zolone (37) 1-phenyl-3-[p-(p-sec. amylbenzoyl)aminobenzoylam1no]-5-pyraz0lone August 19, 1941.

(3 8) 1 -m-tolyl-3- [mfi-phenylpropionyl) aminobenzoylamino] -5-pyrazolone (39) 1-m-tolyl-3- 2,4-di-tert. butyl-m-tolyl-oxyacetylamino) -5-pyrazolone YELLOW COUPLERS (46) p-(w-Benzoylacetamino)benzenesulfonamide (47) pw-Benzoylacetamino) benzensulfon-N-methylamide (48) p-(w-Benzoylacetamino)benzenesulfonanilide (49) 4-benzenesulfonamino-w-benzoylacetanilide (50) 4-(p-toluenesulfonamino -w-benzoylacetanili de (5 1 4- p-laurylbenzenesulfonamino -w-benzoylacetanilide V (52) 1,4-di [p-(benzoylacetamino)benzenesulfonamino] benzene (5 3 N,N-di- (p-benzoylacetaminophenyl) benzene-l 3- disulfonamide (5 4) N- (p-benzoylacetaminophenyl) -4- [p- (benzoylacet-v amino) -benzenesulfonamido benzenesulfonamide (55 N -benzoylacetyl-N'- (Z-benzothiazolyl) sulfanilamide (5 6) p-Acetoacetaminobenzenesulfon-B-naphthalide (57 p-Furoylacetaminobenzenesulfon-N-cyclohexyl amide 5 8) p-(4-ethoxybenzoylacetamino)benzenesulfonamide (59 )v Terephthaloyl-bis (p-N-amylsulfonamide) acet'anilide] (60) p-Quinoline-8-sulfonamino -w-benzoylacetanilide (61) p-Acetoacetamino-o-methylbenzenesulfon N- anilide (62) N,N-di- (p-benzoylacetaminophenol)naphthalene- 1,5-disulfonamide (63 p-(Ben zenesulfonamino)benzoylacetone (64) N-benzoylaceto-o-anisidine g in a photographic developer for producing, a black-and- White negative image, given at leastone more-exposure and then developed at least once more in a photographic developer containing a color coupler to produce acolored image, the colored image bearing a complementary relationship to the region of the spectrumto which the photographic silver halide emulsion had been diflerentially sensitized. The silver produced during development is removed in the usual manner, a ferricyanide solution being suitable. The resulting color images have increased dye density as compared to images prepared from comparable multilayer photographic elements not having alltyl acrylate-acrylic acid'copolymers in the silver halide emulsion layers. If the color coupleris utilized with the alkyl acrylateaacrylic. acid copolymer in the silver halide emulsionlayers in lieu of'inthe color dcveloper composition, the resulting color images do not have'increased dye density. I p v i The invention is illustrated bythe ples of preferred embodiments thereof.

7 EXAMPLE I following examacid. .The copolymer was the Water-soluble ammonium The present process has utility in increasing the dye uppermost blue-sensitive layer. -Such multilayer photo-' graphic elements can also, of course, have other interlayers for specialized purposes. Color formers or color couplers are not utilized in the emulsion layers of the color photographic elements processed in accordance with the invention. Such multilayer materials have previously been described in the art, reference being made to Mannes et al.,- US. Patent .No. 2,252,718; issued In carrying outthe photographic reversal color process-of the invention with an exposed, multilayer photographic element containing a" plurality of differentially sensitized photographic silver halide emulsion'layers as acid copolymer, the photographic element is developed saltand contained about Zilmol percent of the acrylic acid moiety. The resulting films'were then exposed for sec- 0nd to a 500 Watt, 3200 K. light source on'an Eastman type Ib sensitometer; then processed as follows.

Processing step: Time Prehardener bath- ;minutes 1. 7 Water Wash do 1 Elon-hydroquinone development d0 3 Water wash do 3 Flash with No. 2 Photoflood from 1 ,meter second 1 Color development L minutes 10 Water Wash do 8 Fix do i 3 Water wash do 5 Drying. (Samples taken for ilver analysis.) Ferricyanide bleach do: 3 Fix do 3 Water wash do 5 Drying. (Samples taken for dye density measurements.)

Table A below summariZes-thesilvercontent and the magenta dye densities for film samples containing gelatin and 50/50 mixtures of gelatinand the ethyl acrylate-- Table p I 7 7 Silver Devel- Percent Copolymer 1n the Gelatin- Magenta Dm ux opedin Color I Oopolymer Emulsion Vehicle v s Developer,

' 1 mg. Ag/it} As can be observed from the data set'out in Table A,

the presence of the copolymer in the emulsion increased the magenta D about 60% although substantiallyno described above and containing an alkyl acrylate-acrylic 4 cated that the copolymerfdid not cause anyshiftjin dye.

due. The increasedmagenta D resultinglwhen. the

The resulting exposed films were gelatin is replaced with varying concentrations of ethyl acrylate-acrylic acid copolymer are summarized by the data set out in Table B.

Table B Percentcopolymer in the gelatin-copolymer emulsion vehicle: Magenta D 0 2.69

The emulsion coatings containing the copolymer as part of the vehicle had greater reversal shoulder speeds than the emulsion coating containing only gelatin as the vehicle. .The use of 50% of the copolymer in the emulsion vehicle gave 0.25 log E more speed than only gelatin in the emulsion vehicle. The various processing solutions had essentially the following compositions;

Water to make 1 liter. pH=8.0.

ELON-HYDROQUINONE DEVELOPER WHITE DEVELOPER) (BLACK-AND- Water to make 1 liter. pH=-6.8.

6 EXAMPLE 11 Gold and sulfur sensitized silver bromoiodide emulsions coated on transparent cellulose acetate film supports were prepared, exposed in a sensitometer and processed as described in Example I excepitthat color developers containing a cyan-forming coupler and a yellowforming coupler were utilized in lieu of the color developer containing a magenta-forming coupler. Vehicles for the silver bromoiodide of gelatin and 50/50'gelatin/ ethyl acryl'ate-acrylic acid copolymer were compared. The copolymer was the Water-soluble ammonium salt and contained about 20 mol percent of the acrylic acid moiety. Data summarizing the increased cyan and yellow dye densities resulting by using the copolymer in the emul- G. Sodium hexametaphosphate 1.0 Sodium sulfite 72.0 N-methyl-p-aminophenol sulfate 5.0 Sodium carbonate H O 36.0 Hydroquinone 2.0 Sodium bromide 2.0 Sodium sulfate l5 .0 Potassium iodide 0.01 Sodium thiocyanate 1.0 Hydroquinone monosulfonate 1.5 Water to make 1 liter. pH=10.4.

I MAGENTA DEVELOPER (COLOR DEVELOPER) I Sodium hexametaphosphate g 0.5- Sodium sulfite g 3.0 4-amino-N-ethyl-3-methyl-N-,B-methylsulfonamidoethylaniline g 6.0 Sodium carbonate H O g 30.0 Sodium bromide g 0.25 1.0% 6-nitrobenzimidazole nitrate cc 2.5 0.1% potassium iodide cc 2.0 Sodium sulfate g 25.0 Citrazinic acid g 3.0 Polyethylene glycol (M. Wt. 1540) g 1.0 Sodium thiocyanate g 4.0 1- (2,4,6-trichlorophenyl -3 a- 4-nitrophenoxyacetamidoJ-S-pyrazolone g 2.0 Water to make 1 liter. pH=1l.0.

FIX

i G. Sodium hexametaphosphate 10.0 Sodium sulfite 10.0 Sodium thiosulfate pentahydrate 320.0 Water to make 1 liter.

FERRICYANIDE BLEACH Sodium hexametaphosphate a 1.0 Potassium ferricyanide 80.0 Sodium bromide L 34.4

sions are set out in Table C below.

Table C Percent Copolyrner in the Gelatin- Cyan Dm Yellow Dmux Copolymer Emulsion Vehicle CYAN DEVELOPER Hydroxylarnine sulfate g 0.5 Sodium hexametaphosphate g 1.0 Sodium sulfite g 10.0 4-amino-N-ethyl-N- fi-hydroxyethyl) m-toluidine g 1 .3 Sodium bromide g 2.5 Sodium sulfate g 60.0 0.1% potassium iodide cc 8.0 1.0% 6-N-itrobenzimidazole nitrate cc 0.03 Sodium thiocyanate g 1.0 2- (0-acetamido-fi-plienylethyl) -1-hydroxy Y naphthamide g 1.45 Hexylene glycol cc 10.00 Monobenzyl-p-aminophenol g 0.4 Polyethylene glycol (M. Wt. 1540) g 1.0 Water to make 1 liter. pH= 12.4.

' YELLOW DEVELOPER Sodium hexametaphosphate g 1.0 Sodium sulfite g 10.0 2-methyl-4-(methylsulfonamide ethyl) ethyl aniline g 2.0 Sodium bromide g 0.7 Sodium sulfate g 64.0

' 0.1% potassium iodide cc 20.0

1.0% 6-nitrobenzimidazole nitrate cc 0.06 10% diethylhydroxylamine oxalate cc 5.0 a-Benzoyl-2-methoxyacetanilide g 2.0 Hexylene glycol cc 20.0 1-phenyl-3-pyrazolidone cc- 0.4 Polyethylene glycol (M. Wt. 6000) g 1.0 Water tojmake 1 liter. pH:12.5.

' EXAMPLE III Several single layer films were prepared with bluepercent of the acrylic acid moiety. Both the sodium salt of the copolymer and the acid copolymer were tested by replacing '10, 30 and 5 0% portions of the gelatin as the The copolymers utilized with silver halide vehicle. The results of the. tests are sum marized by the data set out in Table D- below.

It is to be noted from the data in Table D that the ethyl acrylate-acrylic acid copolymers significantlyv increased the magenta dye density in the color reversal image. The copolymer which was substituted for varying amounts of the gelatin in the silver halide vehicle did not reduce the speed of the emulsion.

EXAMPLE IV A multilayer color film comprising a cellulose acetate support containing superimposed silvergelatino-bromoiodide emulsion layers differentially sensitized to blue, green and red light as described in Mannes et al., US.

Patent No. 2,252,718, issued August 19, 1941,1is improved with respect to yellow, magenta and cyan densities respectively when 50% of the gelatin :vehicle in each of the three diilerentially sensitized emulsion layers is replaced with the ethyl acrylate-acrylic acid copolymer'described in Example I, and when processed in accordance with the Mannes et al. reversal color process.

The above examples illustrate the improved dye densities resulting when silver' halide emulsions having mixtures of gelatin and alkyl acrylate-acrylic acid copolymers as vehicles are processed with reversal color processes utilizing color couplers or color formers in the color developers. lized in the emulsions, and the resulting emulsions are subjected to reversal color processing, increased dye densities do not result as illustrated in Example V below.

7 EXAMPLE .V A water soluble sodium salt of an ethyl acrylate-acrylic However; when the color couplers are uti-' E 7 Sodium sulfite, anhydrous s s g- 50.0 Hydroquinone g 6.0. Sodium carbonate monohydrate ;g 35.0 Potassium bromide g 2.0 Sodium thiocyanate g 1.5

acid copolymer containing about 201x101 percent ofthe J acr lic acid moiet was incor orated in var in re or-' tions in several high-speed'silver-bromoiodide emulsions differentially sensitized to. blue, green and red light. The

McCrossen et al. US. Patent 2,875,057 in dibutyl phthal- The emulsions sensitive in the green range contained dispersed therein a pyrazolone coupler suitablefor ate,

forming a magenta image with oxidized color developer, e.g. couplers Nos. 7 etc-of Eierke et al. US. Patent 2,810,-

171 (column 2). The emulsions sensitive in. the red range contained dispersed therein a phenolic coupler suitable for forming a cyan image with oxidized color developer, e.g.

couplers No. l to 6 ofFi'erke et al. US. Patent 2,801,171 ,(column 2) in a. solvent such as tri-o-cresyl phosphate.

Emulsions containing none of the copolymer addenda were also prepared. The emulsions were then coated on a transparent cellulose acetate film support, dried, exposed in an Eastman lb Sensitometer and thereafter processed in a reversal color process as follows. v

' The exposed films were developed in a developer hav- 7 ing the following composition:

Sodium hexametaphosphate g N-rnethyl-p-arninophenol sulfate g 0.5% solution of 6-nitrobenzimidazolenitrate cc 12.0 0.1 solutionof potassium iodide cc 10.0 \Vater to malse 1 liter.

The elements were then thoroughlywashedawith water and treated ..in a hardening ,bat'n havingtheQfollowing composition: ,.1. 7

Potassium chrome alum crystals 'g 30.0'

Waterto make 1 liter. 1 i

The elements were then thoroughly washed with water and flashed with white light for a period sufiicient to'ex pose residual silver halide. The elements were then treated in a color developer having the following com-.

Sodiumhydroxide Color developer 1 Ethylenediamine sulfate Citrazinic acid Water tomake 1 liter.

1 d-arnino-N-ethyl-N-(B methanesulfonamidoethyl)m-toluidine sesquisulfate monohydrate.

The elements were then thoroughly washed with water Water to make 1 liter.

The elements were then treated in a bleach bath having the following composition:

. v G. Potassium dichrornate 5.0 Potassium ferricyanide -d 70.0 Potassium bromide. 20.0

Water to make 1 liter.

The-elements were again washed and treatedonce again with the clearing and fixing bath identified above. The elementswere again washed and treated in a stabilizing bath having the following composition:

Formaldehyde (37% by weight) cc 7.0

Dispersing' agent 1 g 0.5

I Water to make 1 liter. 7

Such as'lriton X100, i.e. an'alk lar 1 01 ether alcohol (octylphenoxy polyethoxy ethanol). y p y Table below summarizes theresults of the tests, data I .concermng D fi D and relative shoulder speed being set outfor each of the. three reversal images.

Table E Percent Copolymer in the Gelatin- I V 1 Relat' Oopolymer Emulsion Vehicle Drain i Dmnx Should? Speed A. Magenta Reversal Image: 7 r i 10 3. 14 100 .19. I 2. s4 71 V phenolic As can be observed from the data set out in Table E, the subject copolymer did not impart an increased, but rather a decreased, dye density to the reversal image when the color former or color coupler was utilized in the emulsion as distinguished from in the color developers as in the process of the invention.

Thus, the present invention provides a new and useful process in the photographic art.

Although the present invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be efiected within the spirit and scope of the invention as described hereinabove and as defined by the appended claims.

I claim:

1. In a photographic reversal color process wherein a photographic element containing at least one photographic silver halide emulsion layer is given a first exposure to produce a latent image therein, a development in a photographic developer for producing a black-and white negative image, exposure to light of a color to which the said first exposed silver halide emulsion layer is sensitive, and an additional development in a photographic color developer for producing a colored image, said color developer containing an aromatic primary amine color developing agent and a photographic color coupler selected from the group consisting of a magentaforming pyrazolone color coupler, a cyan-forming color coupler and a yellow-forming openchain ketomethylene color coupler, the improvement which comprises utilizing a vehicle for said silver halide comprised of gelatin and a water-soluble lower alkyl acrylate-acrylic acid copolymer having to 50 mol percent of the acrylic acid moiety and wherein said vehicle contains about 1 to 90 percent of said copolymer based on the combined weight of said gelatin and said copolymer.

2. In a photographic reversal color process wherein a photographic element containing at least one photographic silver halide emulsion layer is given a first eX- posure to produce a latent image therein, a development in a photographic developer for producing a black-andwhite negative image, exposure to light of a color to which the said first exposed silver halide emulsion layer is sensitive, and an additional development in a photographic color developer for producing a colored image, said color developer containing an aromatic primary amine color developing agent and a photographic color coupler selected from the group consisting of a magenta-forming pyrazolone color coupler, a cyan-forming phenolic color coupler and a yellow-forming open-chain ketomethylene color coupler, the improvement which comprises utilizing a vehicle for said silver halide comprised of gelatin and a water-soluble lower alkyl acrylate-acrylic acid copolymer having 10 to 50 mol percent of the acrylic acid moiety and wherein said vehicle contains about 10 to 50 percent of said copolymer based on the combined weight of said gelatin and said copolymer.

3. The process as described in claim 2 wherein the alkyl acrylate is ethyl acrylate.

lii

4. The process as described in claim 2 wherein the copolymer comprises about 20 mol percent of the acrylic acid moiety.

5. The process as described in claim 2 wherein the copolymer is utilized as a water-soluble sflt thereof.

6. The process as described in claim 2 wherein the copolymer is utilized in acid form.

7. The process as described in claim 2 wherein the photographic color coupler is a magenta-forming pyrazolone color coupler.

8. The process as described in claim 2 wherein the photographic color coupler is a cyan-forming phenolic color coupler.

9. The process as described in claim 2 wherein the photographic color coupler is a yellow-forming openchain ketomethylene color coupler.

10. In-a photographic reversal color process wherein a multilayer photographic element containing a plurality of photographic silver halide emulsion layers differentially sensitized to difierent regions of the spectrum are given a first exposure to form latent images therein, developing in a photographic developer for producing black-and-white negative images, successively exposing said silver halide emulsion layers to light of a color to which they are sensitive, and after each of the said successive exposures developing in a photographic color developer containing an aromatic primary amine color developing agent and a color coupler for producing a colored image bearing a complementary relationship to the region of the spectrum to which the said color-developed silver halide emulsion layer had been diirerentitially sensitized, said color coupler being selected from the group consisting of a magenta-forming pyrazolone color coupler, a cyan-forming phenolic color coupler and a yellow-forming open-chain ketomethylene color coupler, the improvement which comprises utilizing a vehicle for said silver halide comprised of gelatin and a water-soluble lower alkyl acrylate-acrylic acid copolymer having 10 to mol percent of the acrylic acid moiety and wherein said vehicle contains about 10 to 50 percent of said copolymer based on the combined weight of said gelatin and said copolymer.

11. The process as described in claim 10 wherein the alkyl acrylate is ethyl acrylate.

12. The process as described in claim 10 wherein the copolymer comprises about 20 mol percent of acrylic acid moiety. 2

13. The process as described in claim 10 wherein the copolymer is utilized as a water-soluble salt thereof.

14. The process as described in claim 10 wherein the copolymer is utilized in acid form.

References Cited in the file of this patent UNITED STATES PATENTS 2,252,718 Mannes et a1. Aug. 19, 1941 2,831,767 Dann et al. Apr. 22, 1958 3,019,104 Oster Ian. 30, 1962 3,062,674 Houck et al. Nov. 6, 1962 

1. IN A PHOTOGRAPHIC REVERSAL COLOR PROCESS WHEREIN A PHOTOGRAPHIC ELEMENT CONTAINING AT LEAST ONE PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER IS GIVEN A FIRST EXPOSURE TO PRODUCE A LATENT IMAGE THEREIN, A DEVELOPMENT IN A PHOTOGRAPHIC DEVELOPER FOR PRODUCING A BLACK-AND WHITE NEGATIVE IMAGE, EXPOSURE TO LIGHT OF A COLOR TO WHICH THE SAID FIRST EXPOSED SILVER HALIDE EMULSION LAYER IS SENSITIVE, AND AN ADDITIONAL DEVELPMENT IN A PHOTOGRAPHIC COLOR DEVELOPER FOR PRODUCING A COLORED IMAGE, SAID COLOR DEVELOPER CONTAINING AN AROMATIC PRIMARY AMINE COLOR DEVELOPING AGENT AND A PHOTOGRAPHIC COLOR COUPLER SELECTED FROM THE GROUP CONSISTING OF A MAGENTAFORMING PYROZOLONE COLOR COUPLER, A CYAN-FORMING PHENOLIC COLOR COUPLER AND A YELLOW-FORMING OPENCHAIN KETOMETHYLENE COLOR COUPLER, THE IMPROVEMENT WHICH COMPRISES UTILIZING A VEHICLE FOR SAID SILVER HALIDE COMPRISED OF GELATIN AND A WATER-SOLUBLE LOWER ALKYL ACRYLATE-ACRYLIC ACID COPOLYMER HAVING 10 TO 50 MOL PERCENT OF THE ACRYLIC ACID MOIETY AND WHEREIN SAID VEHICLE CONTAINS ABOUT 1 TO 90 PERCENT OF SAID COPOLYMER BASED ON THE COMBINED WEIGHT OF SAID GELATIN AND SAID COPOLYMER. 